High Conversion of Concentrated Sugars to 5-Hydroxymethylfurfural over a Metal-free Carbon Catalyst: Role of Glucose-Fructose Dimers.

To reduce the production cost of chemicals from renewable resources, the feedstock loading must be high and the catalyst must be of low cost and efficient. In this study, at a very short reaction time of 10 min at 125 °C, concentrated sugar solutions (20 wt %, 101 wt % on solvent) were converted to 5-hydroxymethylfurfural (HMF) over a cotton gin trash (CGT)-derived sulfonated carbon catalyst in a 1-butyl-3-methyl-imidazolium chloride ([BMIM]Cl) and 2-methyltetrahydrofuran (MeTHF) biphasic system. We report, for the first time, that the presence of glucose either as a covalently bonded monomer in sucrose or in a mixture with fructose achieved yields of HMF up to 62 mol % compared to a value of only 39 mol % obtained with fructose on its own. In the concentrated reaction medium, glucose, fructose, and sucrose molecules produce difructose anhydrides, dimers/reversion products, and sucrose isomers. The glucose-fructose dimers formed in sucrose and glucose/fructose reaction systems play a critical role in the transformation of the sugars to a higher-than-expected HMF yield. Thus, a strategy of using cellulosic glucose, where it is partially converted to fructose content and the high sugar concentration sugar mixture is then converted to HMF, should be exploited for future biorefineries.

Selective depolymerization of sugarcane bagasse anaerobic digestate to highly stable phenols-rich bio-oil with the iron-doped K-feldspar catalyst.

Sustainable implementation of thermochemical conversion of biomass to targeted products is dependent on innovations in catalyst design and tuning of structure-property relationships. This study details the use of potassium feldspar (K-feldspar) as a support doped with different iron (Fe) concentrations via wet impregnation (WI) method for hydrothermal liquefaction (HTL) of sugarcane bagasse anaerobic digestate. The Fe/K-feldspar supported catalysts were synthesized and characterized using X-ray diffraction, Inductively Coupled Plasma Optical Emission spectroscopy, Brunauer-Emmet-Teller and Scanning Electron Microscopy analytical methods. Amongst all the catalysts, K-feldspar dopped with 10 wt% Fe (WI-10) was more effective, producing 51.2 wt% bio-crude. The catalyst's activity has been related to the balanced proportion of the microcline: sanidine: haematite (2.8:3.3:1) phases of Fe present on the catalyst, the surface area (porosity), and the surface functionality, thus conferring desirable activity properties. In addition, the WI-10 catalyst had a better selectivity towards substituted phenols that can potentially be used for higher-value applications such as the production of Nylons 6 and 66, and bioplastics. The bio-oil produced with WI-10 has also been demonstrated to be highly stable. The catalyst was reusable up to four times maintaining moderate catalytic performance, and a simple regeneration protocol was shown to restore the activity of the catalyst. The resulting solid residue also exhibited promise as a viable material for use in electrodes for Lithium-ion batteries (LiB). Therefore, this research has demonstrated a promising and sustainable resource recovery strategy for valorising wet biomass wastes into streams of useful products for valuable chemical production and energy application.

Conversion of agricultural waste into stable biocrude using spinel oxide catalysts.

Biomass, the feedstock for biocrude and ultimately renewable diesel is a low energy density feedstock. The transport of this feedstock over long distance has been proven to be a major burden on the commercialisation of biorefining. Therefore, it has been generally accepted that biomass should be upgraded to biocrude (a relatively high energy density liquid) in close proximity to the biomass sources. The biocrude liquid would then be transported to a biorefinery. Biocrude contains large amounts of oxygen (generally up to 38 wt%) that is removed from the crude in the refining process. In this study, we have synthesised a range of spinel oxide based catalysts to remove oxygen from the biocrude during the catalytic fast pyrolysis. The activity of spinel oxide (MgB2O4 where B = Fe, Al, Cr, Ga, La, Y, In) catalysts were screened for the pyrolysis reaction. While all the tested spinel oxides deoxygenated the pyrolysis vapour, MgCr2O4 was found to be effective in terms of oxygen removal efficiency relative to the quantity of bio oil produced.

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid.

Achieving the goal of living in a sustainable and greener society, will need the chemical industry to move away from petroleum-based refineries to bio-refineries. This aim can be achieved by using biomass as the feedstock to produce platform chemicals. A platform chemical, 2,5-furandicarboxylic acid (FDCA) has gained much attention in recent years because of its chemical attributes as it can be used to produce green polymers such polyethylene 2,5-furandicarboxylate (PEF) that is an alternative to polyethylene terephthalate (PET) produced from fossil fuel. Typically, 5-(hydroxymethyl)furfural (HMF), an intermediate product of the acid dehydration of sugars, can be used as a precursor for the production of FDCA, and this transformation reaction has been extensively studied using both homogeneous and heterogeneous catalysts in different reaction media such as basic, neutral, and acidic media. In addition to the use of catalysts, conversion of HMF to FDCA occurs in the presence of oxidants such as air, O2, H2O2, and t-BuOOH. Among them, O2 has been the preferred oxidant due to its low cost and availability. However, due to the low stability of HMF and high processing cost to convert HMF to FDCA, researchers are studying the direct conversion of carbohydrates and biomass using both a single- and multi-phase approach for FDCA production. As there are issues arising from FDCA purification, much attention is now being paid to produce FDCA derivatives such as 2, 5-furandicarboxylic acid dimethyl ester (FDCDM) to circumvent these problems. Despite these technical barriers, what is pivotal to achieve in a cost-effective manner high yields of FDCA and derivatives, is the design of highly efficient, stable, and selective multi-functional catalysts. In this review, we summarize in detail the advances in the reaction chemistry, catalysts, and operating conditions for FDCA production from sugars and carbohydrates.

Red-mud based porous nanocatalysts for valorisation of municipal solid waste.

Red mud samples were used to catalyse in-situ co-pyrolysis of pinewood and low-density polyethylene for the production of high-quality bio-oil. The sodium cation in the crude red-mud was exchanged with barium and calcium cations and further tested to explore their role in oil upgrading. The relationship between red-mud catalytic activity and its constituents was explored using synthetic sodalite. The red-mud catalysts exhibited a considerable aromatisation capacity compared to the thermal co-pyrolysis, as the selectivity towards monocyclic aromatic hydrocarbons increased from 12.7 to 19.6%, respectively. Long-chain molecules cracking was more significant in synthetic sodalite associated with their acidic active sites. The addition of barium and calcium cations to the red-mud largely improved oxygen elimination as a result of the enhanced catalyst basicity. In contrast, the aromatisation ability of red-mud significantly impeded by the large cation size (Ba2+ and Ca2+) due to the limited diffusion of pyrolysis vapours to the active sites. Ba-exchanged red-mud catalysts reduced the content of carboxylic acids in the bio-oil to 1.8 % while maintained a high yield of the organic fraction (34 %). Ca-exchanged red-mud catalysts produced the lowest fraction of oxygenated compounds (35.1 %); however, the organic phase yield was as low as 23.6 %. The modified red-mud catalysts reduced the fraction of oxygenated compounds from 69.9-35.1% during the biomass-plastic co-pyrolysis.

Effect of HCOOK/Ethanol on Fe/HUSY, Ni/HUSY, and Ni-Fe/HUSY Catalysts on Lignin Depolymerization to Benzyl Alcohols and Bioaromatics.

We have investigated the production of benzyl alcohols and bioaromatics via the reductive lignin depolymerization process over Fe/H-style ultrastable Y (HUSY), Ni/HUSY, and Ni-Fe/HUSY catalysts using HCOOK/ETOH in air. Synergy effect between HCOOK and the catalysts improved the depolymerization process, resulting in a higher bio-oil recovery. HCOOK does not act solely as an in situ hydrogen source; it also interacts with lignin to enable its initial depolymerization via a base-catalyzed mechanism to low-molecular-weight fragments, and in tandem with the catalyst, the hydrogenolysis rate of the depolymerized lignin monomers was enhanced. Fe/HUSY displayed an excellent activity for the catalytic reductive step in contrast to Ni/HUSY and Ni-Fe/HUSY by facilitating methoxy group removal via hydrogenolysis, thereby contributing to the yield and stabilization of the low-molecular-weight aromatics [diethyl ether (DEE)-soluble products]. Fe/HUSY gave the highest DEE product yield of >99 wt % and a total benzyl alcohol yield of 16 wt % with a total selectivity of 47 wt % (60 wt % for aromatic alcohols). Fe/HUSY was reused for the lignin depolymerization reaction without much loss of its initial activity, giving 13 wt % yield of benzyl alcohols with a selectivity of 58 wt % (77 wt % for aromatic alcohols).

Highly active and robust Ni-MoS2 supported on mesoporous carbon: a nanocatalyst for hydrodeoxygenation reactions.

NiMoS2 nanoparticles supported on carbon, synthesized by a microemulsion method were used as a nanocatalyst for hydrodeoxygenation (HDO) of a lignin model compound - guaiacol. Two types of carbon supports - mesoporous carbon (CMK-3) and activated carbon (AC) with a predominantly microporous structure, were studied to investigate the role of porosity and nature of the porous structure in catalyst activity. The activity of NiMoS2/AC resulted in the complete guaiacol conversion at 13 h of reaction time to produce phenol (31.5 mol%) and cyclohexane (35.7 mol%) as the two main products. Contrastingly, NiMoS2/CMK-3 needed a much lesser reaction time (6 h) to attain a similar conversion of guaiacol but gave different selectivities of phenol (25 mol%) and cyclohexane (55.5 mol%). Increased cyclohexane production with NiMoS2/CMK-3 implied better deoxygenation of MoS2 and enhanced hydrogenation capacity of Ni since phenol is a partially deoxygenated product of guaiacol while cyclohexane is a completely deoxygenated and hydrogenated product. The superior catalytic activity and deoxygenating behavior of NiMoS2/CMK-3 catalysts could be attributed to the organized mesoporosity of the CMK-3 support in relation to the improved active phase distribution and access to active sites that facilitate the conversion of the reaction's product. Recyclability study implied NiMoS2/CMK-3 was more stable without significant changes in the catalytic activity even after three reaction cycles.

Direct Production of 5-Hydroxymethylfurfural via Catalytic Conversion of Simple and Complex Sugars over Phosphated TiO2.

A water-THF biphasic system containing N-methyl-2-pyrrolidone (NMP) was found to enable the efficient synthesis of 5-hydroxymethylfurfural (HMF) from a variety of sugars (simple to complex) using phosphated TiO2 as a catalyst. Fructose and glucose were selectively converted to HMF resulting in 98 % and 90 % yield, respectively, at 175 °C. Cellobiose and sucrose also gave rise to high HMF yields of 94 % and 98 %, respectively, at 180 °C. Other sugar variants such as starch (potato and rice) and cellulose were also investigated. The yields of HMF from starch (80-85 %) were high, whereas cellulose resulted in a modest yield of 33 %. Direct transformation of cellulose to HMF in significant yield (86 %) was assisted by mechanocatalytic depolymerization-ball milling of acid-impregnated cellulose. This effectively reduced cellulose crystallinity and particle size, forming soluble cello-oligomers; this is responsible for the enhanced substrate-catalytic sites contact and subsequent rate of HMF formation. During catalyst recyclability, P-TiO2 was observed to be reusable for four cycles without any loss in activity. We also investigated the conversion of the cello-oligomers to HMF in a continuous flow reactor. Good HMF yield (53 %) was achieved using a water-methyl isobutyl ketone+NMP biphasic system.